CN101959973A - Comprise the particle and the application thereof of nuclear and shell - Google Patents
Comprise the particle and the application thereof of nuclear and shell Download PDFInfo
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- CN101959973A CN101959973A CN2008801117354A CN200880111735A CN101959973A CN 101959973 A CN101959973 A CN 101959973A CN 2008801117354 A CN2008801117354 A CN 2008801117354A CN 200880111735 A CN200880111735 A CN 200880111735A CN 101959973 A CN101959973 A CN 101959973A
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
Abstract
The present invention relates to comprise the particle of nuclear and shell, prepare method, the various uses of described particle and the various products that comprise described particle of described particle.Can be used as photocatalyst, antiseptic-germicide, sanitising agent, antifogging agent and decomposition agent according to particle of the present invention.In addition, this particle also can be applicable to solar cell.
Description
Invention field
The present invention relates to comprise the particle of nuclear and shell, prepare method, the multiple use of described particle and the multiple product that comprises described particle of described particle.
Background of invention
It is well-known with the particle of shell to comprise nuclear.
US2007/187463A1 discloses the semiconductor particle of the nano-scale with core/shell structure, wherein each particle all comprises nuclear and shell, and demonstrate following feature: average particulate size is no more than 100nm, and the variation factor of nuclear distribution of sizes is no more than 30%.
Yet these particles are typically much smaller than 100nm, and do not comprise nuclear and dielectric or the semi-conductive shell of conduction.
WO2007/086267A1 discloses the semi-conductor nano particles with core/shell structure, and wherein the ratio of the particle diameter of thickness of the shell and nuclear part is the optimum value for the required optical property of optical element.The described thickness that contains the semi-conductor nano particles mesochite part of core/shell structure is not more than 1/2nd of nuclear part particle diameter.The particle diameter of nuclear part is 0.2nm or bigger less than the thickness of 20nm and shell part.Selectively, the particle diameter of nuclear part is that the thickness of 20-100nm and shell part is at least 1/100 of nuclear part particle diameter.Examine partly to comprise and be selected from B, C, N, Al, Si, P, S, Zn, Ga, Ge, As, Se, Cd, In, at least a element among Sb and the Te.Being characterized as of this semi-conductor nano particles comprises the bigger composition of a kind of ratio nuclear part band gap in its shell part.
Yet these particles do not comprise nuclear and dielectric or the semi-conductive shell of conduction typically much smaller than 100nm.
WO2005/100426A1 discloses a kind of nanoparticle of core-shell type and has prepared the method for this particle, the method for the insulating film of the low dielectric of the described particle preparation of a kind of usefulness, and the insulating film of prepared thus low dielectric.More specifically, the nanoparticle of this disclosure of the Invention comprises: have cancellated organic polymer nuclear particle, and around the shell-layer that forms by the silsesquioxane prepolymer of this nuclear particle.In addition, the method for preparing these nanoparticles has also been described.
JP2006224036 discloses a kind of new photocatalyst and the method for light-catalyzed reaction, and it can effectively carry out for example light-catalyzed reaction of organic compounds containing nitrogen.Described photocatalyst possesses the nuclear of being made up of semi-conductor nano particles, and is covered in the shell of this nuclear by the space, and comprises the controlled core/shell structure body of shell internal voids.Light-catalyzed reaction (methyl alcohol be the dehydration reaction of substrate except) is by being carried out through electronics and/or positive hole that illumination produces by semi-conductor nano particles.This nuclear comprises at least two kinds of nanoparticle complex bodys that available is different, and they combine with semi-conductor nano particles and catalyst nanoparticles.
This invents unexposed particle with space.In addition, this particle is typically very little, does not comprise nuclear and dielectric or the semi-conductive shell of conduction, and comprises the nuclear with at least two kinds of different subjects.
CN1792445 discloses a kind of composite catalyst of nano semiconductor type, and it is served as reasons as the sulfide of nuclear or selenide with as the TiO of the coating of shell
2The semi-conductor nano particles that layer is formed.Its preparation method comprises for example following step: utilize wet chemistry method and surfactant-modified legal system to be equipped with Cadmium Sulfide (or cadmium selenide) nanoparticle of high dispersive, the organic pure titanium of ultrasonic hydrolysis is to obtain TiO
2, and TiO
2And the physical bond between Cadmium Sulfide (or cadmium selenide) nanoparticle.It has high photocatalytic activity and stability.
This file is not explained size of particles, the shell nuclear of unexposed conduction and dielectric or semi-conductive.
US6,908,881B1 disclose a kind of under radiation of visible light activated catalyzer, this catalyzer is a kind of oxide semiconductor with stable oxygen defect, for example anatase titanium dioxide.The method of preparation activated catalyzer under radiation of visible light also is provided, this method comprises by utilizing hydrogen plasma or rare gas element plasma body to handle oxide semiconductor, is included in essentially no air and invades under the state of treatment system and carry out described processing.Disclose a kind of goods, these goods are included in the base material that its surface provides above-mentioned catalyzer, also disclose the method for decomposed substance, and this method comprises makes the target resolvent contact under illumination with above-mentioned catalyzer, and this illumination has visible radiation at least.A kind of novel photocatalyst that makes the using visible light radiation become possible is provided, and has utilized this photocatalyst to remove the various methods that contain the material of organism or bacterium by photolysis.
Yet this invention is not at particle but at oxide semiconductor layer.
US2004/258762A1 discloses a kind of particulate, and this particulate comprises crosslinked protein shell, and the top coat that connects by covalent linkage.
Yet this application is not explained the wherein electrology characteristic of disclosed particle.This particulate is used to optical contrast agents.In addition, this invention does not relate to the shell that comprises optional cross-linked proteins.
US2004/245496A1 discloses a kind of new sanitising agent, and this sanitising agent comprises by TiO
x(1.5＜x＜2), TiO
xN
2-x(1＜x＜2), diamond-like carbon, and titanium oxide-silica composite TiO
x-SiO
2At least a component in the group that (1.5＜x＜=2) are formed, and the method for the described sanitising agent article-cleaning of a kind of usefulness.This invention further provides a kind of anti-biotic material that comprises above-mentioned materials, a kind of antimicrobial product with same characteristic, a kind of method of production environment material, a kind of new function sorbent material and production method thereof.
Yet size of particles is typically much smaller than 100nm.In addition, TiO
xRelative quantity will be far above the present invention.
JP2003/064278 discloses nuclear-shell semi-conductor nano particles, and this particle has photo catalytic reduction ability and the dispersiveness in organic substrate simultaneously, and the resin combination that makes with this particle is provided.This nuclear-shell semi-conductor nano particles comprises having the core-shell particles that the number average size of particles is 2-50nm, and this particle comprises the semiconductor nanocrystal as nuclear, and in its surface bonding the conductor of finishing molecule is arranged as shell.
Yet the size of described particle is usually less than 100nm.In addition, the feature of this particle is not really clear and definite.
DE 101 64 768 A1 disclose core-shell particles (I), and this particle has as the size of particles of nuclear less than the inorganic nano-particle of 100nm and inorganic oxide as shell, and the most of ground of described particle, and does not preferably reunite fully.Independent power requires also to comprise following content: (1) core-shell particles (II), its size of particles that is used as nuclear is less than the inorganic nano-particle of 100nm and inorganic oxide/oxyhydroxide preparation as shell, its mesochite is by change pH and use a kind of wet-chemical reaction of enzyme to provide, and the gained powder is calcined after removing solvent; Similar core-shell particles (III), it comprises as the size of particles of nuclear less than the inorganic semiconductor nanoparticle of 100nm and metal as shell; (2) (III) type core-shell particles, its mesochite are to utilize metal ion on the semiconductor surface by light-initiated redox reaction preparation, and the gained powder is calcined after removing solvent.
Yet the shell of this particle is an electroconductibility, and nuclear is semi-conductivity, and its size of particles is much smaller than the present invention.
Multiple in these particles all has photolytic activity, and can therefore be used as photocatalyst.This photolytic activity typically can be by owing to well-known photocatalyst TiO
2Existence.Yet, TiO
2Can only when existing, the UV radiation use as photocatalyst.Therefore its use is restricted.
Had wherein by changing TiO
2Structure improve TiO
2Active embodiment is suggested.Yet these improve and all do not relate to particle.
As described, titanium dioxide (TiO
2) be a kind of well-known photocatalyst that is used under ultraviolet (UV) light, particularly its anatase octahedrite demonstrates the photocatalytic activity that is higher than the rutile phase mutually.The mixture of having reported a kind of anatase octahedrite and rutile recently has the activity higher than pure anatase octahedrite.
In addition, TiO
2Be a kind of very strong oxygenant and can water of decomposition, being about to water splitting is oxygen (O
2) and hydrogen (H
2).This is attributable to the strong oxidation potential in positive hole in the catalyzer.We notice that hydrogen can be used as fuel, thereby TiO
2Have the use potentiality in producing the energy.
TiO
2But also direct oxidation organic materials.Work as TiO
2Just become hydrophilic further when being exposed in the UV light, therefore can use it for antifogging coating or self-cleaning window, rely on TiO wherein
2Can remove organism effectively.In addition, with TiO
2Sneak into and significantly to reduce for example concentration of volatile organic compounds and oxynitride of airborne pollutant in the outdoor building material.
TiO
2Therefore be added into coating, cement, window, brick and tile, or in the other products so that sterilization to be provided, deodorizing and antifouling performance also can be used as hydrolyst simultaneously.TiO
2Can also use in the Graetzel battery, this battery is a class electrochemistry solar cell.
It should be noted that anatase octahedrite is not TiO mutually
2The most stable phase.Rutile is TiO mutually
2In the most general natural form.Therefore preparation is a problem keeping for more time anatase octahedrite at many-side anatase octahedrite all preferably mutually and further mutually.
Water and air all is that tellurian life is necessary, but according to UN, does not have the tap water of safety above 1,100,000,000 population in developing country.In addition, 2,000,000,000 populations do not possess enough sanitary facilitys.According to WHO, the death that 400 60 ten thousand populations are arranged every year is directly owing to atmospheric pollution equally.Therefore, clean water and air and suitable sanitary facility are most important basic living conditions on the earth.At present ways of addressing this issue is usually too expensive, and is low with regard to active speech efficient, can't utilize and complexity too.Thereby still exist for the demand that further addresses these problems and limit its consequence.
Puppet emits commodity can cause the massive losses of tax revenue, and the while also can jeopardize people's health owing to for example counterfeit drug.This situation every year is all in phenomenal growth.Therefore anti-counterfeiting technology all becomes extremely important in increasing product.That latest developments have been got up is a kind of " having the coating (Cpuf) that physics can not copy function ", and this Cpuf is a kind of unique on IC and the compound coating that can't duplicate.About the composition of coated material, TiN for example, TiO
2, monoaluminum phosphate (MAP) and some dielectric materialss have been submitted several patents to, US6198155B1 for example, US 6759736B2 and WO03/046986A2.Particle being distributed on the IC at random described dielectric or conduction.Can there be the sensor network of being made by the Al electrode in top at IC.The randomness of this particle distribution has caused has multiple electric capacity on the IC.This just provides a kind of aforesaid fingerprint that is difficult to duplicate.
Yet hacking technique is all improving every year, thereby Q-character level that need improve constantly and improved security.
Some above-mentioned particles exist other problem, when needs, and too low or even the disappearance of the chemical/physical activity of this particle.And further problem is its activity even is subject to for example irradiation of UV light.In addition, most above-mentioned materials does not have the character of conduction and/or dielectric and/or semi-conductive and/or structure, and is necessary in the described hereinafter application of these character.
Yet very difficulty maybe can't prepare such particle at present: this particle has the nuclear and the shell of differing materials; And/or described particle is little, but is not again too little for some application, and promptly the gravel size decision ground of its center is greater than 100nm and preferably less than 100 μ m; And/or described particle is stable, for example, do not change in time automatically, do not carry out phase transformation, and is stable in environment for use, or the like.
In addition, be difficult to maybe can't prepare the roughly particulate of homogeneous of nuclear size and thickness of the shell, particularly the less situation of thickness of the shell wherein.Whenever thickness of the shell becomes hour, shell typically trends towards having open space in shell.Equally, this shell typically comprises such zone, and this zone is not subjected to processing when chemical treatment, promptly remains to handle preceding state, and comprises preferably processed zone, and promptly its thickness is thick much larger than average shell.
Therefore the objective of the invention is to solve one or more above-mentioned problems.
Summary of the invention
First aspect in invention discloses a kind of particle that comprises nuclear and shell, its center comprises first kind of material conduction or semi-conductive, its mesochite comprises second kind of material dielectric or semi-conductive, the composition of wherein said second kind of material is different from the composition of described first kind of material, described thickness of the shell is greater than 10nm, be preferably more than 30nm, more preferably greater than 50nm, and wherein thickness of the shell is less than 200nm, and its center gravel size decision ground is greater than 100nm, more preferably greater than 150nm, even more preferably greater than 250nm, even more preferably greater than 500nm, most preferably greater than 1000nm, and the gravel size decision ground of its center is less than 100 μ m, more preferably less than 50 μ m, even more preferably less than 25 μ m, even more preferably less than 10 μ m, most preferably less than 3 μ m.
Surprisingly, the invention provides solution for above problem.In addition, in the time can using, also improved the performance of core-shell particles aspect one or more.This solution also makes following application become feasible: still can not or be at most at present the application with limited form.
In preferred embodiments, the variation of the relative thickness of shell is less than ± 20%, and preferably less than ± 10%, more preferably less than ± 5%, it is further improved and establishes by the optimization method condition.Therefore, for the particle of dimensional change, for example the particle of size from 300nm to 1500nm obtains for example thickness of the shell of 30nm ± 5nm for all particles.These facts measure definite by TEM and EDS.
In preferred embodiments, the shell that has the nuclear that accounts for the 0.1-99.9999% volume and account for the 99.9%-0.0001% volume according to particle of the present invention.
Described particle can comprise: have the nuclear of first kind of electro-conductive material and have the shell of second kind of dielectric materials, or have the nuclear of first kind of semiconductive material and have the shell of second kind of dielectric materials, or have the nuclear of first kind of electro-conductive material and have the shell of second kind of semiconductor material, or have the nuclear of first kind of semiconductive material and have the shell of second kind of semiconductor material, second kind of material is different from described first kind of material.One or more embodiments depend on to be used and by preferred.For example, under light-catalysed or chemically active particle situation, endorse, comprise for example material of TiN, and shell can be for example TiO of semiconductor material to be electroconductibility
2-X, described this particle also can be used for forging, and under the situation of " forgery " particle, endorses to be electroconductibility, comprise the material of TiN for example or TaN or metal, and shell can be for example TiO of dielectric materials
2, perhaps endorse being semi-conductive for example Si, and shell can be for example SiO of dielectric materials
2, perhaps endorse being semi-conductive for example GaAs or GaN, and shell can be semiconductor material for example InP or InAs.
The different evident difference that mean at first kind of material and second kind of storeroom composition.Thereby, the particle that comprises first kind of (nuclear) material, its nuclear is outside to be formed because the radiation of for example high energy particle produces slight variation, thus form since different phases or owing to the formation in dislocation or room differentiable shell, described particle is not included into scope of the present invention.Typically, nuclear of the present invention is different with the chemical constitution of shell, thereby causes described nuclear to have different physics and/or chemical feature respectively with shell, for example different electrical characteristics, different chemically reactives, perhaps different stability.
For satisfying for example photolytic activity of some aspect of the present invention, the thickness of shell is subjected to strict boundary constraint, for example owing to wish to exist outward appearance to be roughly the nuclear of black (face as follows).Thickness as shell is too little or too thick, and this effect has just disappeared.Typically, shell can have the thickness of 5nm to 200nm in these cases, as 10nm, or 20nm, or 100nm.
Nuclear mainly comprises first kind of Ti compound and its mesochite mainly comprises under the situation of second kind of Ti compound therein, for different application, and for example photolytic activity and chemically reactive, this shell can have the thickness greater than 5nm, and the size of nuclear can be greater than 10nm.Typically, more little particle in needing chemically active application, may show good more.
In order to reach best effect, particle can not be too big, because the ratio of such useful area and volume will reduce.Particle can not be too little.Obviously can make the physical size of particle adapt to the purposes of imagining, and this point is one of advantage of the present invention.Thereby size of particles, and the thickness proportion of nuclear and shell can be for each purposes or purposes and optimize.
The further advantage of particle of the present invention is to use simple, cost is low, their characteristic can design in the scope of broad, can imagine to adapt to different purposes, efficient, their high reactivities in various fields, nontoxic relatively and environmental friendliness, and they are all stablized in time and in various environment.
As an example of programmable characteristic, in the specific absorption of a certain wavelength, and the activity that therefore also has them, can change (face as follows) by the relative quantity of adjusting shell.
Wavelength design makes the possibility that becomes that combines with prior art especially like this.If for example in conjunction with silicon and particle of the present invention, just can increase the efficient of solar cell, this is because the absorption in bigger wavelength region and the generation of electronics.
Further advantage is that particle of the present invention demonstrates strong activity under daylight.Thereby not needing other source of radiation for example situation and the place of UV light in that daylight is arranged, it is feasible that many application all become.This causes running cost very low, because this operation does not need or the further energy of limited ground needs.
Typical embodiment, its application also has thereby the advantage of acquisition will become clearer by ensuing description and embodiment.
In preferred embodiments, first kind of material comprises and is selected from Ti, Al, Hf, Zr, Sr, Si, Ta, transition metal (the 3rd (IIIB) be to 12 (IIB) family, Ac system except) is Fe and Zn for example, Si, Ge, C, Ga, As, In, Cd, Ba, or the element in its combination, preferably this material comprises Ti.
In preferred embodiments, second kind of material comprises and is selected from Ti, Zn, Al, Hf, Ga, Cu, Sr, Zr, Si, In, Ga, Ba, or the element in its combination, preferred Ti or SrTi, or BaTi, most preferably Ti.
In preferred embodiments, first kind of material further comprises and is used for compensating first kind of element valence, is selected from C, N, O, P, As, Sb, Se, Te, S, or the element in its combination, preferred N.
In preferred embodiments, second kind of material further comprises and is used for compensating first kind of element valence, is selected from C, N, P, As, Sb, O, S, Se, Te, F, Cl and organic group, or the element in its combination, preferred O.
Again, depend on and want the feature that obtains and the purposes of imagination, can carry out multiple combination.These combinations can be optimized for the purposes of imagination, therefore the present invention can be used widely.
Typical first kind of material is TiN, transition metal (the 3rd (IIIB) be to 12 (IIB) family, Ac system except), Al, TaN, and semi-conductor (IV:Si, Ge, C, SiC, SiGe; III-V:GaAs, GaN, GaP, GaSb, InP, InAs, InSb, InN, II-VI:ZnSe, ZnO, ZnS, ZnTe, CdS, CdSe CdTe), and has O
2The titanate in room, for example TiO
2, SrTiO
3, BaTiO
3, PbTiO
3, and typical second kind of material is TiO
2, any dielectric materials metal oxide for example, nitride, fluorochemical, muriate and organic dielectric materials, and also can be above-mentioned semiconductor material arbitrarily.
In preferred embodiments, particle according to the present invention has the TiO of comprising
2Shell with comprise the nuclear of TiN.
Thereby, the photolytic activity that preferably demonstrates, and/or chemically reactive, and/or cleaning action, and/or the particle of antimicrobial acivity is: (nuclear/shell) TiN/TiO
2-xOr conductor material or semiconductor material, TiN for example, Ti, Al, Hf, Zr, Fe, Si, Ge, C, Au, Pt, Ag, Sr, Zn, Ta, Ni, Cu, SiGe, GaAs, GaN, GaP, GaSb, InP, InAs, InSb, InN, ZnSe, ZnO, ZnS, CdS, CdSe has TiO respectively
2Shell; Conductor material and its conductor oxidate, Zn/ZnO for example, Fe/FeO
xPerhaps conductor material or semiconductor material Si for example, Ge, C, SiC, SiGe, GaAs, GaN, GaP, GaSb, InP, InAs/InSb, InN, ZnSe, ZnS, CdS, CdSe, TiN has the ZnO shell respectively; Perhaps conductor material or semiconductor material Si for example, Ge, C, SiC, SiGe, GaAs, GaN, GaP, GaSb, InP, InAs/InSb, InN, ZnSe, ZnS, CdS, CdSe, TiN has SrTiO respectively
3Shell; Perhaps conductor material or semiconductor material TiN for example, Ti, Al, Hf, Zr, Fe, Si, Ge, C, SiC, Au, Pt, Ag, Sr, Zn, Ta, Ni, Cu, SiC, SiGe, GaAs, GaN, GaP, GaSb, InP, InAs, InSb, InN, ZnSe, ZnO, ZnS, CdS, CdSe has FeO respectively
xShell; Perhaps has TiO
2Semiconductor material, or have ZnO, SrTiO respectively
3, FeO
xSemiconductor material.
Thereby the particle of the Cpuf feature that preferably demonstrates is: (nuclear/shell) TiN/TiO
2, or metal and its dielectric oxide or conductor oxidate, Cu/CuO or one of above-mentioned for example, or dielectric materials and its metal.Nuclear part can be conductor material and semiconductor material arbitrarily, transition metal (the 3rd (IIIB) to 12 (IIB) family, Ac system except) for example, Al, TiN, TaN and semi-conductor (IV:Si, Ge, C, SiC, SiGe; III-V:GaAs, GaN, GaP, GaSb, InP, InAs, InSb, InN, II-VI:ZnSe, ZnO, ZnS, CdS, CdS) and have an O
2Titanate (the TiO in room
2, SrTiO
3, BaTiO
3, PbTiO
3).Its example is above providing.
The shell part can be any dielectric materials, for example metal oxide, nitride, fluorochemical, muriate and organic dielectric materials.Also can be semiconductor material (as mentioned above) with conductive core.
The method for preparing core-shell particles can comprise: oxidation, and nitrogenize is fluoridized and the chlorination particle surface, perhaps uses sol-gel method, hydrothermal method, spraying-desiccating method, spraying-pyrolysis method, the freeze-dried method, plasma spraying method or the like is coat on particle.
Under the situation of oxidized metal surface, typical core-shell particles is: Al nuclear and Al
2O
3Shell, adulterated Si nuclear and SiO
2Shell, Cu nuclear and CuO shell, Ta nuclear and Ta
2O
5Shell, and TiN nuclear and TiO
2Shell.Under the situation of coating, metal core and oxide coating are preferred.
The size of particles that preferably demonstrates good Cpuf feature depends on the design of electrode when being used to use and interelectrode distance when assembling.For example, if two interelectrode distances are 2 μ m, then size of particles should be greater than 1 μ m and less than 2 μ m.Thereby between adjacent two electrodes, particle is arranged sometimes, and do not have particle between those electrodes, to occur sometimes, but particle may appear at above the electrode.Therefore, size of particles is typically greater than 0.2 μ m, is preferably more than 0.2 μ m, but less than 3 μ m.
Disclose the method for preparation according to particle of the present invention in a second aspect of the present invention, the method comprising the steps of:
I) provide and comprise the first kind of electro-conductive material forming nuclear or the particle of semiconductor material,
Ii) form the shell that comprises second kind of dielectric materials or semiconductor material around nuclear, the thickness of its mesochite is preferably more than 30nm greater than 10nm, more preferably greater than 50nm.
The method for preparing core-shell particles can comprise: oxidation, and nitrogenize is fluoridized, sulfuration, selenizing and chlorination particle surface perhaps use sol-gel method, hydrothermal method, spraying-desiccating method, spraying-pyrolysis method, the freeze-dried method, plasma spraying method or the like is coat on particle.
Under the situation of oxidized metal surface, typical core-shell particles can be Al nuclear and Al
2O
3Shell, adulterated Si nuclear and SiO
2Shell, Cu nuclear and CuO, Ta nuclear and Ta
2O
5, and TiN and TiO
2Under situation about applying, metal core and oxide coating are preferred.
In preferred embodiments, first kind of electro-conductive material comprises TiN, and wherein second kind of dielectric materials comprises TiO
2, wherein at step I i) in first kind of electro-conductive material comprising O
2Atmosphere in heating surpass 15min, reach and be higher than 400 ℃ temperature.
Purposes according to particle of the present invention, for example TiN/TiO are disclosed in a third aspect of the present invention
2As photocatalyst, its mesochite is semi-conductive, and wherein this photocatalyst can by from about 300nm to the radioactivation about 850nm wavelength.Thereby, except wavelength region the UV radiation in the about about 400nm of 300nm-interval, catalyzer of the present invention can also be by the wavelength radiation activation from about 600-850nm, perhaps by wavelength radiation activation from about 400-600nm, perhaps activated by the source of radiation of specific wavelength, or its combination, for example xenon lamp or sunlight.
By design nuclear relative quantity and the composition thereof with shell, for example by changing the thickness of shell, composition of nuclear and shell or the like can be so that wherein particle demonstrates improved photoabsorption and/or active wavelength region may is more suitable.Particle can be absorbed in the light of following wavelength as a result: for example at the bigger wavelength in IR district, or at wavelength from for example 400-600nm, and perhaps at the littler wavelength in UV district, or its combination.According to an example of photocatalyst of the present invention, it comprises 16% TiO
2, demonstrate in zone absorption more than several percentage ratios from 300nm to 900nm almost, in zone from 450nm to 800nm almost more than 20% absorption, and in regional from about 480nm to about 680nm more than 80% absorption.This particle comprises for example TiN and TiO
2
Disclose a kind of photocatalyst that comprises according to particle of the present invention in the present invention aspect further, its mesochite is semi-conductive.This particle comprises for example TiN and TiO
2
A kind of equipment that comprises according to photocatalyst of the present invention is disclosed in the present invention aspect further.This equipment can be chemical reactor or solar cell.
Disclose the purposes of particle according to the present invention as chemical reagent in the further embodiment of the present invention, this reagent can water of decomposition.Therefore water be broken down into H
2And O
2This characteristics of decomposition can be used for producing H
2, and H
2Obviously be the energy of for example a kind of cleaning.
Disclose a kind of purposes of particle according to the present invention as chemical reagent in the further embodiment of the present invention, this reagent can be with organism, for example acetaldehyde, dirt, organic solvent, tensio-active agent, agrochemicals, environmental pollutant, and smell is decomposed into for example littler compound such as H
2O, CO
2, and/or this reagent can reducing compound phenylformic acid for example, carbonic acid gas and NO
xThis particle comprises for example TiN and TiO
2
Disclose the purposes of particle according to the present invention as chemical reagent in the further embodiment of the present invention, this reagent can serve as antifog material.This particle comprises for example TiN and TiO
2
Disclose the purposes of particle according to the present invention in safety coatings in the further embodiment of the present invention, its mesochite is a dielectricity.Typically, a kind of coating that comprises according to particle of the present invention, the information that protection is stored on its lower chip is not replicated, and reads or misapplies, and perhaps this coating self produces password.Like this, conductor material is embedded dielectric materials.This particle comprises for example TiN and TiO
2
As mentioned above, surprisingly can produce by reproducible mode, the essential feature that adapts to desired use is provided according to particle of the present invention.
The advantage of this particle is:
The increase of effective dielectric constant lateral variation on the-circuit,
-composition and nuclear that they can depend on nuclear-shell respectively provides different effective dielectric constants with the thickness of shell, and
-a lot of materials can be used for target (objected) purposes.
The purposes of particle according to the present invention in solar cell disclosed in the further embodiment of the present invention.
Disclose the solar cell that comprises according to particle of the present invention in the present invention aspect further, its mesochite is semi-conductive.This particle comprises for example TiN and TiO
2
The equipment that comprises according to solar cell of the present invention is disclosed in the present invention aspect further.
Solar cell is partly to replace one of most promising clear energy sources of fossil oil.Yet Si solar cell still expensive (economic amortization) and with other energy specific efficiency is not high mutually.In addition, produce solar cell and consume lot of energy, and need from solar cell, to regain for many years the energy (environment amortization) of this quantity.Carried out at present much about reducing cost and improving the research of solar battery efficiency.For example film Si technology and dye sensitization solar battery can be used as the selection that reduces cost.Yet their efficient is all not really high.Use the multiple joint solar cell of compound semiconductor to provide and be higher than 40% efficient, but since compound semiconductor materials and integrated cost they are very expensive.For traditional energy being changed into substitute energy such as solar cell, need solution cheaper and that efficient is higher.Can find the different methods of raising the efficiency such as upconverter and low-converter in the literature, have the semi-conductor of different energy gaps, the hot carrier battery.But these solar cells are all very expensive and consume lot of energy aborning.
We have described a kind of very cost-effective and very efficient method of producing energy from sunlight in this application.Under being reluctant to accept by the situation of restraining, the inventor believes can be electric energy or hydrogen and oxygen (chemical energy) with energy transformation.One of principal character that it is believed that the application is the influence of the thickness of particle shell to its outward appearance.If it is too thick that its shell becomes, the color of particle becomes for example yellow from black.As a result, the absorption of light is restricted, for example, because be not that all or most of wavelength that wherein exists can be absorbed.Thereby this particle efficient in energy transformation reduces.Thickness as shell becomes too little, beginning explict occurrence slit in the shell, and the result will not have (visible) light to be absorbed in these slits.By changing the thickness of shell, can be designed aspect wavelength/energy specific absorption region.So the nanoparticle with different diameter and different thickness of the shells can be used to add wide absorption spectrum and thereby raising energy conversion efficiency.
The contriver believes, is being reluctant to accept under the contained situation of opinion, and the thickness of shell is subjected to strict boundary constraint, for example, owing to wish to exist surface plasma and/or quantum limit.Thickness as shell is too thin or too thick, and this effect has just disappeared.Typically, shell can have the thickness of 5nm to 200nm in these cases, as 10nm, or 20nm, or 100nm.In addition, must satisfy the conservation of momentum.So the nanoparticle with different diameter can be used to add wide absorption spectrum and thereby raising energy conversion efficiency.
In order further to improve its uptake rate and absorption spectrum, can provide dyestuff in nanoparticle surface.This dye molecule is known in the literature, for example organic Ru title complex.
The advantage of described solar cell is:
-than the cheaper and simple method of standard P N junction type solar cell,
-higher than the efficient of colloid photocatalyst and Si solar cell,
-might integrated several stratified semiconductor materials adding wide absorption spectrum,
-produce this equipment than Si solar cell needs energy (environment is more friendly) still less
Coating or the film that comprises according to particle of the present invention disclosed of the present invention aspect further.For example, particle is offered in the coating of base material substrate surface.Described base material is the exterior wall of for example building, the outside surface of roof or top ceiling, the outside surface of window glass or internal surface, the interior wall in house, floor or top ceiling, window shutter, curtain, the protective wall of motorway, interior wall in the tunnel, the outerplanar of head light or the plane of reflection, the internal surface of the vehicles, the perhaps plane of mirror.Described coating provides and the same or analogous advantage of particle that exists.This coating can be used according to standard technique.This particle comprises for example TiN and TiO
2
A kind of equipment that comprises according to coating of the present invention is disclosed of the present invention aspect further.Clearly, the part that described coating can forming device.
A kind of chemical reagent that comprises according to particle of the present invention is disclosed of the present invention aspect further.This reagent can be the form of solution, particulate form, the perhaps form of liquid.This particle comprises for example TiN and TiO
2
A kind of equipment that comprises according to chemical reagent of the present invention is disclosed of the present invention aspect further.This equipment can be waste water plant, aircleaning facility, and sanitation, this equipment decomposes the pollutent that partly or entirely is present in the there.
The purposes of particle according to the present invention in system for producing hydrogen disclosed of the present invention aspect further.Owing to for example TiO
2Can from water, produce H
2, the different embodiment of particle of the present invention can be used for described purpose.
In a kind of germ-resistant purposes that discloses aspect further according to particle of the present invention of the present invention.This equipment can be waste water plant, aircleaning facility, and sanitation, this equipment decomposes bacterium and/or the fungi that partly or entirely is present in the there.
So clearly, advantage of the present invention is:
-very efficient antibacterial effect is because eliminate bacterium near 100% with the unusual this powder (50mg/l) of lower concentration in 5min
In the purposes that discloses aspect further according to particle of the present invention of the present invention as sanitising agent.This particle is closely related with kill microorganisms and decomposition agent as the principle of work of sanitising agent.This particle comprises for example TiN and TiO
2
This particle also shows effect of Combination.Thereby this particle can be used to purify waste water and/or air, wherein efficient pollutent and the eliminating bacteria of removing of while.Advantage is:
-a kind of under large-scale visible light (house is inner or outside), purifying air and the cheap and simple method of water,
The TiO of filtration of-ratio and/or standard
2Photocatalysis Decomposition pollutent efficient is higher,
-make different sizes and structure easily.
Particle according to the present invention may reside in the concentration interval of 5-40mg/L, 10-30mg/L for example, perhaps 10
-5-5*10
-1Gr/cm
2Be capped area, for example 10
-4-10
-1Gr/cm
2, preferably 10
-3-5*10
-2Gr/cm
2Typically, this particle should cover the zone of light source, thereby the quantity of particle also depends on the size of particle.In order to make film from powder, such film can comprise particle tackiness agent connected to one another, but in order to optimize the efficient of film, preferably should not have material to remain between powder after the preparation film.Pt can be improved the efficient of this powder as photocatalyst as additive.Depend in addition and expect that using the component that can also exist is: filler, solvent, stablizer, levelling agent, emulsifying agent.
A kind of particle that is obtained by the method according to this invention disclosed aspect further of the present invention.
The following examples are in order to illustrate different aspect of the present invention.These embodiment also are not meant to limit the present invention in any manner.
In addition, it should be apparent to those skilled in the art that different embodiment combinations also also within the scope of the present invention by expection.
The accompanying drawing summary
Fig. 1 is the crystalline structure of the TiN powder of oxidation.
Fig. 2 is TiO
2Amount at O
2And N
2O in the gaseous mixture
2
Fig. 3 is TiO
2Amount to the amount of initial TiN powder.
Fig. 4 is the XRD diffractogram of TiN powder.
Fig. 5 is the TEM and the EDS result of the TiN powder of oxidation.
Fig. 6 is the crystalline structure of the TiN powder of oxidation.
Fig. 7 is TiN nuclear-TiO
2The optical absorption spectra of shell powder.
Fig. 8 is the decomposition that is exposed to AO behind the halogen lamp.
Fig. 9 is the amount that is exposed to bacterium death in the halogen lamp artifact film.
Figure 10 is TiN nuclear-TiO
2The photocatalyst of shell.
Figure 11 is the TiO of sinuous comb structure
2-type photocatalyst (X-cross section).
Figure 12 is the TiO of sinuous comb structure
2-type photocatalyst (on-down, structure 1).
Figure 13 is the synoptic diagram of water/purifying air.
Figure 14 is the greatzel battery.
Figure 15 is the core-shell particles in the coating.
Embodiment describes in detail
Embodiment
The oxidation of embodiment 1TiN.
With the TiN powder at O
2In in 400-600 ℃ of thermal treatment 1 hour.1.45g and the TiN powder of 0.25g is all 500 ℃ of beginning oxidations.The TiN powder is the rutile phase by the anatase octahedrite inversion of phases of complete oxidation and existence in the time of 600 ℃.500 ℃ is the optimal temperature that obtains the maximum anatase octahedrite in the described scope.
Fig. 1 is presented at the O in the mixed gas
2(%) for the influence of the crystalline structure of the TiN powder of oxidation.For the TiN powder of 0.25g, anatase octahedrite mainly is formed at the O of 4-19%
2, for the TiN powder of 1.45g, anatase octahedrite mainly is formed at the O of 2-6%
2According to Fig. 1 and 2, contain the TiO of the 20 weight % that have an appointment (for example 15-25 weight %)
2Sample have anatase octahedrite as principal phase at the TiN powder surface.
Fig. 3 has shown that the TiN amount of powder is for forming TiO
2The influence of amount.The TiN powder heated 1 hour in 500 ℃ in 2 kinds of different atmosphere.Contain 5% O in the mixed gas
2The time, for oxide compound as the about 20 weight % of TiN output of 0.25,1.45,10 and 21g of raw material powder.Can on TiN nuclear, provide a large amount of anatase octahedrites in 1 hour in 500 ℃ of thermal treatments under this environment.
According to XRD figure (Fig. 4), oxidizing reaction depends on the amount of TiN powder, and promptly how the TiN powder is filled in the container, as the tamped density of the height and the powder of powder filler.This is because this oxidizing reaction is thermopositive reaction.If the TiN powder of oxidation 1.45g, this powder are principal phase by complete oxidation and rutile then.If yet the TiN powder of oxidation 0.25g forms TiN nuclear and TiO
2Shell, wherein anatase octahedrite is principal phase (Fig. 5).
Temperature when oxidizing reaction also depends on thermal treatment and atmosphere have been carried out the optimum condition that main formation anatase octahedrite is sought in some experiments for this reason.Fig. 6 has shown the crystalline structure of the TiN powder of oxidation.
Embodiment 2TiN nuclear-TiO
2The shell powder is to the absorption of light.
Fig. 7 is TiN nuclear-TiO
2The optical absorption spectra of shell powder.TiN by 4% and 96% TiO
2The powder absorption of forming is higher than UV light, and (wavelength (λ)＜387nm) is lower than the light of 550nm, and this yes.In addition, by 84%TiN and 16%TiO
2The powder of forming absorbs the light that is lower than 850nm.Two kinds of powder, the powder of particularly high TiN content all absorbs large-scale visible light (λ＞387nm).
Embodiment 3TiN nuclear-TiO
2The photocatalytic activity of shell powder.
The appraisal procedure of the photocatalytic activity of these powder is that (400＜λ＜850) photodegradation is often used as the organic compound acid orange 7 (AO7) of azoic dyestuff under halogen lamp.Is the TiN nuclear-TiO of 5-100mg/l with the AO7-aqueous solution (20mg/1) of 2ml with concentration
2Shell powder-aqueous solution.It should be noted that because the anti-degradation property that they are specially designed is difficult to decompose azoic dyestuff usually.Yet Fig. 8 has shown and is being exposed to halogen lamp two kinds of powder AO7 that can degrade especially apace after next hour.This phenomenon demonstrates the very strong photocatalytic activity of particle of the present invention.
Light-catalyzed reaction depends on very doughtily from the distance of light source and the surface-area of used powder.The solution that contains the lower concentration powder demonstrates higher relatively photodegradation speed.This can cause the long-pending reduction of powder surface, the perhaps scattering of light that causes owing to particle owing to reunion.
Embodiment 4TiN nuclear-TiO
2The anti-microbial activity of shell powder.
Use Streptococcus mutans (Streptococcus mutans) ATCC 700610 as bacterium, it is cultivated 8h in 37 ℃ in as test organic brain heart infusion (BHI) nutrient solution.This culture of 0.5ml is mixed with the BHI+2% sucrose of 25ml, and the suspension equal portions of 0.2ml are added in the aseptic hole of 96 orifice plates.This plate is at 37 ℃ of incubation 16h.Form sticking bacterial layer (microbial film) in the bottom in hole.Subsequently the BHI substratum is removed from microbial film and add TiN/TiO
2Powder suspension (50mg/l).The hole is exposed the different time periods under halogen lamp.Use to live/dead (Live/dead) fluorescence viability staining agent, determine the mortality ratio of bacterium by fluorescent microscope.Fig. 9 is presented at and exposes 5min, the TiN by 4% and 96% TiO under the halogen lamp
2The powder of forming has just killed the bacterium near 100%, and by 84% TiN and 16% TiO
2The powder of forming then through 15min just kill can be extremely near 100% bacterium.Use pure TiO
2Can't reach high like this kill ratio fully.
A kind of simple mode is to use according to TiN nuclear-TiO of the present invention
2The shell powder is made vesicular structure (Figure 10) in the sedimentary substrate of Pt.Yet, it should be noted that this method may be difficult to make enough water to arrive the Pt surface.In order to address this problem, what have the hole comprises TiN nuclear-TiO
2The beam of the nanostructure of shell powder is a kind of possibility.Figure 11 has shown two kinds of dissimilar sinuous comb structures.Structure 1 is made up of the beam of the layered catalyst of insulation layer supports in the substrate.This layered catalyst uses TiO
2As top light active coating, TiO
2Perhaps directly on Pt, perhaps at TiO
2And dye sensitizing agent arranged between the Pt.Here Pt plays the work that helps catalytic reducer in order to increase the hydrogen that forms from water.TiO
2Only in the UV optical range, show as photocatalyst, yet dye sensitizing agent is expanded absorb light to visible-range.Other metal can replace Pt to use as reductive agent.Not only inorganic materials but also organic materials can use as insulation layer, for example silicon-dioxide (SiO
2), silicon nitride (Si
3N
4) and Resins, epoxy.With a kind of TiN nuclear-TiO
2Shell powder photocatalyst replaces TiO
2, and do not have dye sensitizing agent.Structure 2 is a kind of photoelectrochemical cells, wherein the TiO at top
2Layer is an anode, and the Pt layer is a negative electrode.Dye sensitizing agent is incorporated into TiO
2The layer and the Pt layer between with the expansion light absorption.Here, TiN nuclear-TiO
2The shell powder also can replace TiO
2Use as photocatalyst.Dye sensitizing agent is not necessary in this case.
In these two kinds of structures, water also can flow between beam and substrate by the hole, and this makes in water cracking and form hydrogen in the Pt side very effectively.
Figure 12 shown on the structure 1-under view.
If the organic materials of evaporation when being used in (200 ℃) under the subzero treatment (for example typical air gap material), or be easy to be dissolved in material preparation hole part in wet cleaning liquor such as acid solution or the alkaline solution, the processing of these structures is simple so.
Another possibility is to use material such as the PMMA that decomposes under comparatively high temps.Perhaps use the SiO that is dissolved in HF solution
2As sacrifice layer, and propping material is to HF inert nitride or other material.
Embodiment 6 usefulness have strainer according to TiN nuclear-TiO of the present invention
2The shell photocatalyst is purified waste water/air.
In order to purify waste water and/or air, will be deposited on the submicron zanjon slot type Si structure according to nuclear of the present invention-shell photocatalyst.Figure 13 shown the structure that proposes on-under with the view in X-cross section.
At first, utilize the Bosch method that this deep trench pattern is added in the Si wafer.Use the spin-coating method will be afterwards, and under inert atmosphere, make it be attached to the Si surface by thermal treatment according to nuclear of the present invention-shell powder deposition at Si wafer top.As shown in the figure, air or water are mobile from the bottom of Si wafer.Have than larger sized particle of slotted eye diameter or material and removed, and the remainder of material pollutent for example by the Si of nanostructure, parasite and bacterium under the inside in for example house or the outside visible light that occurs by TiN nuclear-TiO
2The shell photocatalyst decomposes and kills.
Embodiment 7 solar cells
It should be noted that in the solar cell in future the nanoparticle of a lot of mean distances each other between 100 nanometers and several microns will be used.Similarly, has different diameter or aspheric nanoparticle also is used.Has wedge angle in the latter case or shaggy more macroparticle also is used.
Preparation TiN/TiO
2The describe, in general terms of the method for powder can find hereinbefore.
The Graetzel battery
The advantage of using Graetzel battery geometry (seeing Figure 14) is not need expensive high-quality semiconductor.This has caused producing a kind of very simple and cost-effective equipment that is used to produce electric energy.Because sufficiently high specific absorption, one deck nanoparticle on the transparency electrode enough forms extremely thin and simple geometric structure.Need redox mediator to make positive charge transfer to counter electrode from nanoparticle.Can cover the reduction that this electrode comes the catalytic oxidation-reduction medium with extremely thin platinum film.Because the catalysis here is surface effects, extremely thin film is enough to guarantee low cost production.
The advantage of above-mentioned solar cell is:
-a kind of use TiN/TiO
2Powder meet very much cost benefit and solar cell very efficiently.Do not need expensive (economically with environment on) crystalline silicon or limited amorphous hydrogenated Si of life-span.
-they are made easily, even make large volume and large size.
A spot of energy requirement provides environment amortization fast in the-manufacture of solar cells.
-in addition, the semiconductor material that surrounds metal nanoparticle has caused high enhancement factor.In the geometry in early days nanoparticle is deposited on the top of solar cell, also utilizes the nanoparticle scattering of light.
The core-shell particles of embodiment 8 in the Puf coating
The compound coating that we have developed being called as on a kind of IC of being coated in " physics can not copy function coating (Cpuf) ".Figure 15 has shown the synoptic diagram of this coating.
The Cpuf of standard is made up of two kinds of different particles; (blueness) and (yellow) in substrate material (left side of Figure 15) of dielectric of conduction.If we replace the particle (centre of Figure 15 and right side) that conducts electricity with the particle of the shell of nuclear that contains conduction and dielectric, the electric capacity of particle will be along with the thickness of shell, the size of nuclear, and nuclear is formed with the material of shell and is changed significantly.This variation has improved the randomness of electric capacity on the circuit.This particle shows as dielectric materials, and it is for example to be modeled as a series of 2 parallel capacitance in AC biasing (AC bias).The thickness of shell is less than size of particles, so this particle has the total capacitance increase of higher relatively k-value and coating.If the shell of this particle shows as semi-conductive or dielectric, depend on thickness, form, crystalline structure and vacancy, it will further increase the randomness of electric capacity.For example, be used for reaching several titanates of above-mentioned target as shell.
Claims (23)
1. particle, comprise nuclear and shell, its center comprises first kind of material conduction or semi-conductive, its mesochite comprises second kind of material dielectric or semi-conductive, the composition of wherein said second kind of material is different with the composition of described first kind of material, the thickness of described shell is greater than 10nm, be preferably greater than 30nm, more preferably greater than 50nm, and the thickness of its mesochite is less than 200nm, the gravel size decision of its center is greater than 100nm, more preferably greater than 150nm, even more preferably greater than 250nm, even more preferably greater than 500nm, most preferably greater than 1000nm, and the gravel size decision of its center is more preferably less than 50 μ m less than 100 μ m, even is more preferably less than 25 μ m, even be more preferably less than 10 μ m, most preferably less than 3 μ m.
2. particle according to claim 1, wherein first kind of material comprises and is selected from Ti, Al, Hf, Zr, Sr, Si, Ta, transition metal (the 3rd (IIIB) be to 12 (IIB) family, Ac system except), Si, Ge, C, Ga, As, In, Zn, Cd, or the element in its combination, preferred Ti.
3. according to claim 1 or 2 described particles, wherein second kind of material comprises and is selected from Ti, Zn, Al, Hf, Ga, Cu, Sr, Zr, Si, In, Ga, Zn, Ba, or the element in its combination, preferred Ti, or SrTi, or BaTi, most preferably Ti.
4. according to any one described particle among the claim 1-3, wherein first kind of material further comprises and is selected from C, N, and O, P, As, Sb, Se, Te, S, or the element in its combination, preferred N, this element is used for compensating the valency of first kind of element.
5. according to any one described particle among the claim 1-4, wherein second kind of material further comprises and is selected from C, N, P, As, Sb, O, S, Se, Te, F, Cl and organic group, or the element in its combination, preferred O, this element is used for compensating the valency of first kind of element.
6. according to any one described particle is as the purposes of photocatalyst among the claim 1-5, its mesochite is semi-conductive.
According to any one described particle among the claim 1-5 as the purposes of chemical reagent, this reagent can water of decomposition.
According to any one described particle among the claim 1-5 as the purposes of chemical reagent, this reagent energy decomposing organic matter, acetaldehyde for example, dirt, organic solvent, tensio-active agent, agrochemicals, environmental pollutant, and smell, and/or this reagent can reducing compound phenylformic acid for example, carbonic acid gas and NO
x
According to any one described particle among the claim 1-5 as the purposes of chemical reagent, this reagent can be as antifog material.
10. according to the purposes of any one described particle in safety coatings among the claim 1-5, wherein said shell is a dielectric.
11. according to the purposes of any one described particle in solar cell among the claim 1-5.
12. comprise coating or film according to any one described particle among the claim 1-5.
13. comprise the solar cell according to any one described particle among the claim 1-5, wherein said shell is semi-conductive.
14. comprise chemical reagent according to any one described particle among the claim 1-5.
15. comprise the photocatalyst according to any one described particle among the claim 1-5, wherein said shell is semi-conductive.
16. comprise the safety coatings according to any one described particle among the claim 1-5, wherein said shell is a dielectric.
17. according to the purposes of any one described particle in system for producing hydrogen among the claim 1-5.
18. according to the purposes of any one described particle in kill microorganisms among the claim 1-5.
19. according to any one described particle among the claim 1-5 as the purposes of sanitising agent.
20. comprise the equipment of coating according to claim 12.
21. comprise the equipment of solar cell according to claim 13.
22. comprise the equipment of chemical reagent according to claim 14.
23. comprise the equipment of photocatalyst according to claim 15.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07118541.7 | 2007-10-16 | ||
| EP07118541 | 2007-10-16 | ||
| PCT/IB2008/054206 WO2009050639A1 (en) | 2007-10-16 | 2008-10-13 | Particle comprising core and shell and applications thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101959973A true CN101959973A (en) | 2011-01-26 |
Family
ID=40263389
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008801117354A Pending CN101959973A (en) | 2007-10-16 | 2008-10-13 | Comprise the particle and the application thereof of nuclear and shell |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20100234209A1 (en) |
| EP (1) | EP2205684A1 (en) |
| CN (1) | CN101959973A (en) |
| WO (1) | WO2009050639A1 (en) |
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| CN102436929A (en) * | 2011-07-22 | 2012-05-02 | 中国科学院上海硅酸盐研究所 | High-dielectric low-loss imitation grain boundary layer capacitor and preparation method thereof |
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| CN105170118A (en) * | 2015-09-30 | 2015-12-23 | 太仓碧奇新材料研发有限公司 | Preparation method of titanium dioxide composite material for removing acid orange II in printing and dyeing wastewater |
| CN109761576A (en) * | 2019-03-20 | 2019-05-17 | 深圳市航天新材科技有限公司 | A kind of functional seal curing agent and preparation method thereof |
| CN111468139A (en) * | 2020-06-10 | 2020-07-31 | 中南大学 | Core-shell structure nanosphere photocatalytic material and preparation method and application thereof |
| CN111468139B (en) * | 2020-06-10 | 2021-08-24 | 中南大学 | Core-shell structure nanosphere photocatalytic material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009050639A1 (en) | 2009-04-23 |
| US20100234209A1 (en) | 2010-09-16 |
| EP2205684A1 (en) | 2010-07-14 |
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